Perfluoroalkyl substituted acrylate monomers and polymers thereof

ABSTRACT

Fluoroalkyl amidoalkyl alcohols of the formula  
                 
are disclosed and their corresponding (meth)acrylate esters. These fluoroalkyl amidoalkyl (meth)acrylate monomers can be copolymerized with a wide variety of conventional ethylenically unsaturated monomers. The resulting copolymers are useful as water, oil- and grease-proofing agents for paper, textiles and hard surfaces such as masonry and wood.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.10/972,944, filed Oct. 25, 2004, currently pending, which claims thebenefit of priority of U.S. Provisional Pat. App. No. 60/514,710, filedOct. 27, 2003. The noted applications are hereby incorporated byreference.

BACKGROUND AND PRIOR ART

The use of perfluoroalkyl—(in the following abbreviated as R_(F))substituted polymers to impart oil and water repellency to a variety ofsubstrates such as textiles and paper is well known. The vast majorityof these polymers are perfluoroalkyl-substituted acrylate copolymersuseful for treating paper and paper products to impart oil and waterrepellency. U.S. Pat. No. 3,919,183 (Jager et al.) discloses polymersuseful as oil repellant coatings for porous substrates such as textilematerials and paper which comprise a perfluoroalkylethyl acrylate. U.S.Pat. No. 4,582,882 (Lynn et al.) describes fluorinated paper sizes whichare copolymers of perfluoroalkyl acrylate. Also U.S. Pat. No. 5,674,961of Fitzgerald discloses fluorochemical polymers useful for water, oiland grease resistance to paper. The monomers used to synthesize theabove perfluoroalkylated polymers are derived exclusively fromR_(F)-substituted alcohols where an ethylene group is present betweenthe R_(F) and the hydroxyl group.

Several patents also describe R_(F)-substituted polyurethanes, forexample U.S. Pat. No. 5,663,273. Polyamide-amino polymers derived frompolyethyleneimine by reaction with esters of perfluoroalkyl-substitutedcarboxylic acids are described in U.S. Pat. Nos. 3,769,307 and3,567,500. These polymers contain a mixture of R_(F)-substituted amideand secondary amino groups. These polymers are used to impartoleophobicity yet hydrophilicity to textile substrates.

Di-R_(F) amidomonocarboxylic acids prepared from 1 equivalent ofdiethylenetriamine, 2 equivalents of an R_(F)-acid and 1 equivalent ofan anhydride are taught for use as textile finishes in U.S. Pat. No.3,754,026. Similar R_(F)-amide-substituted polyethyleneimines useful aschemically resistant surfactants are described in U.S. Pat. No.3,271,430. They are obtained by reaction of a perfluorinated alkanoicacid with a large excess of ethyleneimine. Reaction products ofR_(F)-substituted acids with polymers bearing pendent primary aminogroups attached to a carbon-carbon backbone by a linking group areclaimed in U.S. Pat. No. 4,606,973 as low surface energy coatings forflat substrates.

U.S. Pat. No. 3,818,074 describes saturated and unsaturated fluorinatedalcohols which can have 2 to 12 methylene groups separating aperfluoroalkyl radical having from three to 12 carbon atoms and thehydroxyl group.

U.S. Pat. No. 3,498,958, discloses perfluoroalkyl amidoalkyl alcoholswhich have 1 to 14 methylene groups separating the perfluoroalkylradical and the amido group, (meth)acrylate esters thereof andcopolymers derived therefrom. The amidoalkyl alcohols are the saturatedanalogues of the amidoalkanols of formula I described below, and areobtained by a different synthetic route.

SUMMARY OF THE INVENTION

One aspect of the present invention is a novel R_(F)-alcohol of formulaI,

whereinR_(F) is a straight or branched-chain perfluoroalkyl group containing 4to 20 carbon atoms,R₂ is hydrogen or an alkyl group with 1 to 4 carbon atoms, andm and n are, independently of each other, an integer from 2 to 11.

This R_(F)-alcohol of formula I is synthesized by reacting a linearterminally unsaturated monocarboxylic acid or its lower ester with anamino alcohol, to form an amide-alkanol. This ethylenically unsaturatedintermediate is then reacted with an R_(F)-iodide under free radicalconditions and the product is then dehydrohalogenated with a base. Thisprocess for the preparation of the perfluoroalkyl amidoalkyl alcohol offormula I proceeds in a high overall yield.

The perfluoroalkyl amidoalkyl alcohol of formula I can be used tosynthesize a variety of fluorinated derivatives by the reaction offluoroalkylamido alcohol I with alcohol reactive compounds.

Another aspect of the present invention is the provision of novelacrylate or methacrylate monomers of formula II

whereinR_(F) is a straight or branched-chain perfluoroalkyl group containing 4to 20 carbon atoms,R₁ is hydrogen or methyl,R₂ is H or an alkyl group with 1 to 4 carbon atoms, andm and n are, independently of each other, an integer from 2 to 11.

Other aspects of the present invention are polymers and copolymersderived from the acrylate or methacrylate monomers of formula II, theiruse to impart water, oil and grease resistance to the resulting treatedpaper, textiles and hard surfaces such as masonry and wood. The residualdouble bond can be used for crosslinking of the final polymer.

Perfluoroalkyl substituents which are attached to a long-chainhydrocarbon moiety, such as an undecylenic group, exhibit improvedsurface activity and improved effectiveness as oil repellents, possiblybecause such long-chain hydrocarbon groups, by their inter-chaininteractions, aid in the orientation of the very poorly interactingR_(F)-groups. Hydrogen bonding through the amido groups in theperfluoroalkyl amide-alkyl moiety further promotes a stable linearalignment of the long hydrocarbon-fluorocarbon chains and therebycontributes to the low free surface energy of coatings required for goodwater and oil repellencies.

DETAILED DISCLOSURE

One aspect of the present invention is provision of a novel fluoroalkylamidoalkyl alcohol of formula I

whereinR_(F) is a straight or branched-chain perfluoroalkyl group containing 4to 20 carbon atoms,R₁ is hydrogen or methyl,R₂ is hydrogen or an alkyl group with 1 to 4 carbon atoms, andm and n, independently of each other, are an integer from 2 to 11.

The perfluoroalkyl moiety R_(F) may be a single perfluoroalkyl group,for example perfluorohexyl, or a mixture of such groups, for example amixture of C₄F₉—, C₆F₁₃—, C₈F₁₇—, C₁₀F₂₁—, C₁₂F₂₅—C₁₄F₂₉— and C₁₆F₃₁—groups.

Preferred compounds according to the present invention include thosewherein R_(F) is saturated and contains 6 to 18 carbon atoms, is fullyfluorinated and contains at least one terminal perfluoromethyl group.Most preferably, R_(F) is a fully fluorinated, linear carbon chain withan average of about 4 to 16 carbon atoms.

Preferably R₂ is hydrogen or an alkyl group with 1 to 2 carbon atoms,preferably 1.

Preferably n is an integer from 2 to 11, preferably 8, and m is aninteger from 2 to 6, especially 2 or 3.

Another aspect of the present invention is the provision of acrylate ormethacrylate ester monomers of formula II

whereinR_(F) is a straight or branched-chain perfluoroalkyl group containing 4to 20 carbon atoms,R₁ is hydrogen or methyl,R₂ is H or an alkyl group with 1 to 4 carbon atoms, andm and n are, independently of each other, an integer from 2 to 11.

The preferences for R₁, R₂, m, n and R_(F) are as previously defined forformula I.

Another aspect of the invention is the preparation of fluorochemicalcopolymers from a monomer mixture comprising a fluoroalkyl amidoalkyl(meth)acrylate monomer of formula II, and the use of thesefluorochemical copolymers as internally or externally applied water,oil- and grease proofing paper sizes which impart, in addition to oilresistance, excellent water resistance.

In one embodiment the copolymers are prepared from an R_(F)-amidoalkyl(meth)acrylate of the formula II and other ethylenically unsaturatedmonomers copolymerized in the following percentages by weight, relativeto the total weight of the copolymers:a) 45-90% by weight of a monomer of formula II

whereinR_(F) is a straight or branched-chain perfluoroalkyl group containing 4to 20 carbon atoms,R₁ is H or CH₃,R₂ is H or an alkyl group with 1 to 4 carbon atoms, andm and n are, independently of each other, an integer from 2 to 11; andb) 5-30% by weight of a monomer of formula III(R₂)₂N—(CH₂)_(k)—X₁—C(═O)—C(R₁)═CH₂  (II)in which the nitrogen atom is partially or completely quaternized or inthe form of a salt andX₁ is O or N(R₂) and whereinR₁ and R₂ are defined as above, each R₂ is the same or different, andk is 2 to 4; andc) 0-10% by weight of at least one copolymerizable nonfluorinated vinylmonomer.

Preferably, R_(F) is a straight chain perfluoroalkyl group with 4-16carbon atoms, X₁ is oxygen, and R₁, R₂ and n are as defined above.

Especially preferred are copolymers in which the monomers arecopolymerized in the following percentages by weight, relative to thetotal weight of the copolymers:

a) 65-85% by weight; b) 5-30% by weight and c) 0-10% by weight.

A mixture of compounds of the formula II with R_(F) chain-lengths of 4to 16 carbon atoms is advantageously employed to prepare the inventivecopolymers. In one especially preferred embodiment the monomer of theformula II used to prepare the polymers of this invention is anR_(F)-acrylate which has a chain-length distribution of R_(F)-chains of13±2% C₆F₁₃, 48±2% C₈F₁₇, 23±2% C₁₀F₂₁ and 1.6% C₁₂F₂₅ or higher.

Preferred compounds of the formula III are N,N-dimethylaminoethyl(meth)acrylate; N,N-diethylaminoethyl (meth)acrylate;N,N-dimethylaminopropyl methacrylamide and N-tert. butylaminoethylmethacrylate and their salts.

Useful as co-monomers (c) are a large number of commercially availableacrylates and methacrylates, as well as styrene; but preferably methylmethacrylate, N-methylol acrylamide, 2-hydroxyethyl methacrylate,acrylic acid, glycidyl methacrylate, vinylidene chloride, vinyl acetate,1-vinyl-2-pyrrolidinone, acrylonitrile, methacrylonitrile, vinylchloride, vinylidene chloride and 1-vinyl-2-pyrrolidinone.

The perfluoroalkyl amidoalkyl alcohol of formula I can be synthesized byreacting a linear terminally unsaturated C₅-C₁₄monocarboxylic acid orits lower ester with an amino alcohol of the formula III

to form an amide-alkanol of the formula Ia

reacting this ethylenically unsaturated intermediate with anR_(F)-iodide using a free radical generating mechanism; thendehydrohalogenating this intermediate with an alkali metal hydroxide,wherein R_(F), R₂, m and n are as defined above.

Preferably the first reaction step is carried out without a solvent, byheating the mixture at a temperature of 40° C. to 180° C. for a periodof about 1 to 5 hours. Linear terminally unsaturated monocarboxylicacids such as 4-pentenoic acid and 10-undecenoic acid are preferred. Ina second step this ethylenically unsaturated intermediate is reactedwith an R_(F)-iodide using a free radical generating mechanism. Theintermediate is then subjected to dehydrohalogenation using an alkalimetal hydroxide such as sodium or potassium hydroxide.

The addition of an R_(F)-iodide to an olefin proceeds readily in thepresence of a free radical initiator such as an azo compound or peroxideat conventional initiation temperatures of 35 to 150° C. However, in thepresence of small amounts of aqueous solutions of sulfite, bisulfite ordithionate ions the reaction proceeds faster and gives high conversions.

The general processing conditions for addition of an R_(F)-iodide to anolefin and subsequent dehydrohalogenation to make the compounds offormula I of this invention are described in greater detail in U.S. Pat.No. 5,919,299.

If desired, solvents can be present during the R_(F)-iodide additionreaction. Non-limiting examples include ketones such as acetone, methylethyl ketone or methyl propyl ketone, esters such as isopropyl acetate,alcohols such as ethanol or butanol, ethers such as dioxane ordi(2-hydroxyethyl)ether, hydrocarbons such as toluene or octane, amidessuch as dimethylformamide and lactams such as N-methylpyrrolidone.

The dehydrohalogenation of the R_(F)-iodide addition product isgenerally carried out in water at 50 to 100° C. by reacting the adductwith a strong inorganic base, such as sodium or potassium hydroxide or astrong organic base such as 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU)over a period of several hours. The product is obtained in thenon-aqueous phase, which can be separated and washed with water. Thesolvent can be stripped off; or the product can be isolated as asolution by allowing a clean phase separation to occur between theaqueous and organic phases, followed by drying the organic phase. Themode of isolation will depend on the specific product. Trans olefins areformed predominately, with the cis-/trans ratio being determined by NMR.

The acrylate or methacrylate monomers of formula II can be prepared bythe reaction of the R_(F)-amide-alkanol with acryloyl or methacryloylchloride in the presence of a base such as triethylamine to trap thehydrogen chloride formed. Other methods such as transesterificationusing a tin catalyst and other procedures can be utilized to synthesizethe acrylate and methacrylate esters of formula II.

The copolymers according to the invention are prepared by free radicalpolymerization of the monomer mixtures described above in an aqueousemulsion or in a solvent. For emulsion polymerization water-solubleco-solvents are commonly used to aid migration of the otherwiseinsoluble R_(F)-monomers through the aqueous phase. Useful co-solventsinclude acetone and methanol. Suitable free radical initiators includeazo compounds and water-soluble peroxides, such as potassium persulfate.In another variation of the polymerization in an aqueous medium, theR_(F)-monomer is first emulsified in water using a surfactant and ahomogenizer, followed by copolymerization with the other monomers.

The preferred method for making the polymers of this invention howeveris solution polymerization. Useful solvents are ketones such as acetone,methyl isobutyl ketone and methyl ethyl ketone, esters such as isopropylacetate, alcohols such as methanol, ethanol and isopropanol, andaromatic hydrocarbons such as toluene.

The polymerization is typically carried out at temperatures of fromabout 50 to 100° C. using a free radical initiator, typically a peroxideor azo compound. Useful initiators include benzoyl peroxide,1,2-azo-bis-isobutyronitrile (AIBN) and 1,2-azo-bis-(2-methylbutanenitrile) (VAZO-67).

A chain-transfer agent can be present, such as an alkyl thiol, inamounts of from 0.01 to 1 mole percent.

After the polymerization is complete, the solution is readilytransformed into a cationic aqueous dispersion or solution by adding anaqueous solution of an organic acid such as acetic acid; and thendistilling off the organic solvent to provide a dispersion or solutionconveniently having a solids content of between 20% and 40% by weight.

The fluorochemical copolymers prepared from a monomer mixture comprisinga fluoroalkyl amidoalkyl (meth)acrylate monomer of formula II accordingto the invention are useful as coatings on porous substrates such aspaper and textiles, or on hard substrates such as wood, metal ormasonry. In the paper industry, their main usefulness is based on theirability to impart oil and grease resistance to paper that is used forfood packaging or for any other type of application where resistance tooily substances is required.

Thus, another aspect of the present invention relates to a method ofimparting oil and grease resistance to paper, which comprisesincorporating an amount of a copolymer according to this invention thatis effective to impart oil and grease resistance into the paper.

The application of the copolymer to paper can either be to the dry paperthrough a coating process via a size-press (external paper sizing) or byaddition of a solution or emulsion of the copolymer to an aqueous pulp(internal paper sizing). The level of application in either case ispreferably in the range of 0.02 to 1% by weight of the copolymer, basedon the weight of the dry paper or pulp, corresponding roughly toincorporation of 0.01 to 0.5% by weight of fluorine into the paper orpulp.

Another aspect of the present invention relates to a method of impartingwater, oil and grease resistance to textile materials, which comprisestreating the fabric with 0.2 to 1.0% by weight of a copolymer accordingto this invention that is effective to impart water, oil and greaseresistance onto the textile materials.

Suitable textile materials include cellulosics, especially cotton,polyamides such as nylon, wool and silk, polyesters and polyolefins andblends thereof such as polyester-cotton blends. In one embodiment thetextile material is a carpet.

Still another aspect of the present invention relates to a method ofimparting oil and grease resistance to hard substrates such as wood,metal or masonry, which comprises applying an amount of a copolymeraccording to this invention that is effective to impart oil and greaseresistance onto the surface of the hard substrate. These waterbornefluorochemical copolymer compositions can be applied to the surface byany convenient ways such as wiping with a sponge or cloth, painting witha brush, spraying, and other means.

The following examples describe certain embodiments of this invention,but the invention is not limited thereto. It should be understood thatnumerous changes to the disclosed embodiments can be made in accordancewith the disclosure herein without departing from the spirit or scope ofthe invention. These examples are therefore not meant to limit the scopeof the invention. Rather, the scope of the invention is to be determinedonly by the appended claims and their equivalents. In these examples allparts given are by weight unless otherwise indicated.

The non-limiting examples illustrate how to synthesize the inventivecopolymers and describe in detail methods of their application tovarious substrates. They also demonstrate the good performance of thecopolymers on the various substrates.

EXAMPLE 1

The perfluoroalkyl amidoalkyl alcohol of formula I is synthesized bycondensation of, e.g. 10-undecenoic acid with an alkanolamine such asethanolamine or propanolamine. The general procedure for the synthesisis given below.

Synthesis of a Perfluoroalkyl Amidoalkyl Alcohol

Into a 100 ml three-necked flask fitted with a mechanical stirrer,thermometer, distillation condenser, 20.2 g (0.107 moles) of10-undecenoic acid is placed. The reaction flask is heated to 50° C.,followed by the slow addition of 9.8 g (0.16 moles) of ethanolamine. Thereaction temperature is slowly increased to 180° C. and held at thistemperature for 4 hours. The progress of the reaction is followed by gaschromatography. After 4 hours 1.8 g (95% of theoretical value) of wateris collected. The reaction mixture is cooled to room temperature; thetan colored product is dissolved in ethanol, and then poured into water.The white precipitate of amidealkanol obtained is filtered, washed withwater and dried to give 24.0 g (Yield=97%) of a white powder.

¹H NMR δ: 5.85 (m, 1H), 5.0 (m, 1H), 4.9 (m, 1H), 3.6 (t, 2H), 3.3 (m,2H), 2.2 (2H), 2.1 (q, 2H), 1.6 (b, 2H), 1.4 (t, 2H), 1.35 (8H) ppm. ¹³CNMR δ: 173, 140, 115, 62, 43, 36, 34, 30, 29.8, 25 ppm.

To a 100 ml three necked flask fitted with a mechanical stirrer,condenser and nitrogen purge inlet; 10.0 g (44 mmoles) of amidealkanolfrom above; 11 g of n-propanol, 5 g of water and 27.0 g (44 mmoles) ofTel AN (DuPont's Zonyl Tel AN with a homologue distribution of 53.0%C₈F₁₇I, 30.6% C₁₀F₂₁I, 11.7% C₁₂F₂₅I, 3.6% C₁₄F₂₉I, and 1.0% C₁₆F₃₃I)are added. The mixture is stirred at about 74° C. To the reactionmixture 0.8 g (4.2 mmoles) of sodium metabisulfite and 0.25 g (1.3mmoles) of VAZO-67 are added. The progress of the reaction is followedby gas chromatography. After 3 hours no Tel AN is detected. At about 50°C., 5.0 g of 50% NaOH solution is added slowly to the contents of theflask and the mixture is stirred at about 70° C. After 3 hours, gaschromatography shows that dehydrohalogenation is complete. The reactionmixture is cooled to 60° C.; then 15.0 g of toluene and 10.0 g of wateris added. After stopping agitation the top product layer is removed andwashed twice with 20.0 g portions of water. The solvent is removed on arotary evaporator. Then the product is dried under high vacuum at 50°C., to give the compound of formula (101)

as a cream colored tacky solid having 48 weight % fluorine.

¹H NMR δ: 6.4 (1H, m), 5.7 (1H, m), 3.6 (2H, m), 3.3 (2H, m), 2.2 (4H,m), 1.6 (2H, b), 1.4 (2H, b), 1.3 (8H) ppm. ¹³C NMR δ: 176, 117 (m), 144(m), 110-120 (multiple lines, CF₃ and CF₂ groups), 61, 26, 43, 37, 33,30.2, 29.9, 27 ppm.

EXAMPLE 2 Synthesis of a Perfluoroalkyl Amidoalkyl Acrylate

To a 100 ml three necked flask fitted with a mechanical stirrer, and acondenser; 8.45 g (11.8 mmoles) of perfluoroalkyl-substituted alcohol(101); 30.0 ml of MIBK, and 2.0 g (20 mmoles) of triethylamine areplaced. To the reaction mixture at 10° C., under nitrogen atmosphere,1.5 g (16.6 mmoles) of acryloyl chloride in 5 ml of MIBK is addedslowly, and then the reaction mixture is stirred at room temperature for5 hours. A saturated aqueous NaCl solution is then added and the mixtureis allowed to settle. The top layer containing the product is removedand then washed once with 30.0 g saturated aqueous NaCl. The solvent isevaporated on a rotary evaporator at 65° C. and then at high vacuum togive 8.2 g (yield=94%) of the compound of formula (102)

as a brown colored solid of formula (101) having 43% fluorine.

EXAMPLE 3

A flask fitted with a reflux condenser, thermometer, and a mechanicalstirrer is charged with 5.0 g (6.37 mmoles) of the perfluoroalkylacrylate of EXAMPLE 2, 2.0 g (10.8 mmoles) N,N-diethyl-aminoethylmethacrylate, 0.2 g (3 mmoles) methyl methacrylate and 5.0 g methylisobutyl ketone. The flask is purged with nitrogen and 0.1 g VAZO-67 isadded. The polymerization is performed by stirring the mixture for 5hours at a temperature between 74 and 78° C. To the polymerizationmixture an aqueous solution of acetic acid (0.1 g acetic acid in 30 gwater) is then added, and the mixture is stirred for 15 minutes. Themixture is then transferred to a round-bottomed flask and methylisobutyl ketone is removed under vacuum, resulting in a yellow aqueouscopolymer solution.

EXAMPLES 4 to 6

The procedure of EXAMPLE 3 is used to prepare EXAMPLES 4 to 6, usingazobisisobutyronitrile as the initiator and the comonomer weight ratioslisted below. Composition of Copolymers, in weight percent Amino MethylEXAMPLE R_(F)-monomer (meth)acrylate methacrylate Other 3 69 28 3 — 4 8317 (DEEM) — — 5 89  5 2 4 (NVP) 6 75 22 3 —DEEM = diethylaminoethyl methacrylateNVP = 1-Vinyl-2-pyrrolidinone

EXAMPLE 6

The procedure of EXAMPLE 3 is repeated, using 2.4 g n-dodecyl mercaptanas chain-transfer agent.

The following example shows the performance of the novel R_(F)-polymersas internal paper sizes.

EXAMPLE 7

The compounds of EXAMPLES 3-6 were tested as described below.

Internal Size Application and Testing:

Paper plates of 10 inch diameter were made on a small scale paperplate-making machine, supplied by the CHINET Company. This machineconsists of a rotating element bearing three radially attached dies, onecalled the “forming die” which in step 1 is immersed in the pulp andthrough which the pulp is filtered onto the plate by vacuum; after a ¼revolution the plate reaches step 2, a die called the “vacuum die” whichmolds and dries the plate by suction and heat, and in two more ¼revolutions reaches two more cross-head dies which further dry the plateby heat. The final dryness of the plate is influenced by the strength ofthe vacuum and the drainage characteristics of the pulp, and by thetemperatures of the various dies. A minimum dryness of at least 94%(i.e. 6% water or less) is desirable, otherwise the paper plates loosewet strength.

In the following experiments these conditions were used:

Machine Settings: 10 inch plates;

Target dryness: 95-96%; vacuum die: 300° F./1.XH: 385° F./2.XH: 375° F.

Wet End:

Pulp supplied by the CHINET Company, 3 pounds/trial run, containing aswet-end chemicals, added in 40 sec intervals to the stirred pulp, inorder of addition:

Nalco 7607—cationic retention aid and coagulant (NALCO CHEM. Co.), 8pounds/ton;

Alkyl-ketene dimer (AKD) Water repellent (HERCULES Corp.), 6 pounds/ton

the fluorochemical polymeric size: calculated to give 0.1 weight % Faddon;

Nalco 625—anionic coagulant (NALCO CHEM. Co.), 1 pound/ton.

Tests: two tests were carried out:

-   -   Hot Saline Solution and Hot Oil test.

Procedure:

-   -   1. Weigh paper plate.    -   2. Pour either 2% saline at 72° C. or Mazola corn oil at 99° C.        onto plate, enough to fully cover surface.    -   3. After 5 minutes, pour off solution, wipe plate dry with paper        towels and reweigh.    -   4. Calculate weight % absorption and rate visually the degree of        penetration (R): R=0=>50%; 1=25-50%; 2=<25%; 3=none.

Percent absorption is the more accurate measure of water/oil holdoutperformance.

The finished plates were tested “off machine”, i.e. shortly after madeand after 24 hours. Plate dryness “off-machine” was determinedgravimetrically.

The test results are shown in the following table. Hot Water Hold-OutHot Oil (2% Saline) Cpd. of % F Hold-Out off machine 24 hrs. Ex. No.added R % abs R % abs R % abs 3 0.07 3 1 15 3 3 3 0.15 3 1 15 3 3

The results demonstrate superior oil and water hold-out performance attwo different fluorine levels.

EXAMPLE 8

The following example shows the usefulness of the novel copolymers asexternal paper sizes.

External Size Application:

The neutralized test solutions are added to a 4% aqueous solution ofpaper maker's starch (Stayco M, oxidized starch, from Staley Corp.) andthen applied to unsized paper by padding (paper dipped through starchsolution, and passed through single nip rollers). The resulting sheetsare dried at ambient conditions for 15 minutes, then 3 minutes at 200°F. (97° C.) in an “Emerson Speed Drier” (heated metal plate with canvascover).

Oil and Grease Resistance Tests:

Oil Kit Test:

The oil repellency of the surface is determined by using the TAPPI UM557 OIL KIT TEST, which consists of determining with which of twelvecastor oil-heptane-toluene mixtures having decreasing surface tensionspenetration occurs within 15 seconds; ratings go from 1, lowest, up to12.

Ralston-Purina (RP2) Test:

Grease resistance is determined with the Ralston-Purina test for petfood materials; RP-2 Test, Ralston-Purina Company, Packaging ReferenceManual Volume 06, Test Methods. In summary: cross-wise creased testpapers are placed over a grid sheet imprinted with 100 squares. Fivegrams of sand are placed in the center of the crease. A mixture ofsynthetic oil and a dye for visualization is pipetted onto the sand andthe samples are maintained at 60° C. for 24 hours. Ratings aredetermined by the percentage of stained grid segments, using at leasttwo samples.

Turpentine Test, according to TAPPI T454 om-94, a preliminary test todetermine rates at which oil or grease can be expected to penetrate thepaper.

Water and Alcohol Resistance Tests

Cobb Size Test:

Water resistance is determined using the Cobb Sizing test, as describedin TAPPI T 441 om-90.

IPA Resistance Test:

In this test drops of isopropanol-water mixtures are placed on paper,and after 3 minutes the under side of the paper is monitored forpenetration; if no penetration has occurred, a mixture with the nexthigher IPA content is applied. The rating is based on the highest % byweight IPA which does not penetrate. Ratings are based on 5% IPAincrements. The results are shown in the following table. Cpd. of OilTurpentine Cobb Size IPA Hold-out Ex. No. % F Kit RP-2 Test Test Test 30.09 8 4x0 1800+ 21 10 4 0.1 10 4x0 1800+ 20 40 P-514¹ 0.12 12 4x0 1800+22 40 P-208² 0.10 10 4x0 1800   72  0 FC-845³ 0.10 10 4X0 1800+ 22   40+¹Ciba Lodyne ® P-514, is a commercial polymeric fluorinated paper sizeavailable from Ciba Specialty Chemicals Corp.²Ciba Lodyne ® P-208E is a commercial phosphate ester fluorinated papersize from Ciba Specialty Chemicals Corp.³Scotchguard ® FC-845 is a commercial polymeric fluorinated paper sizefrom 3M Corp.

1. An alcohol of formula I,

wherein R_(F) is a straight or branched-chain perfluoroalkyl groupcontaining 4 to 20 carbon atoms, R₂ is hydrogen or an alkyl group with 1to 4 carbon atoms, and m and n are, independently of each other, aninteger from 2 to
 11. 2. An alcohol according to claim 1, wherein R_(F)is saturated and contains 6 to 18 carbon atoms, is fully fluorinated andcontains at least one terminal perfluoromethyl group.
 3. An alcoholaccording to claim 1, wherein, R_(F) is a fully fluorinated, linearcarbon chain with an average of about 4 to 16 carbon atoms, R₂ ishydrogen or an alkyl group with 1 to 2 carbon atoms, n is an integerfrom 5 to 10, and m is an integer from 2 to
 6. 4. An alcohol accordingto claim 3, wherein R_(F) is a fully fluorinated, linear carbon chainwith an average of about 4 to 16 carbon atoms, R₂ is hydrogen, n is 8,and m is an integer from 2 to
 3. 5. A process for the preparation of analcohol according to claim 1, which comprises a) reacting a linearterminally unsaturated C₅-C₁₄monocarboxylic acid or its lower ester withan amino alcohol of the formula III

to form an amide-alkanol of the formula Ia

b) reacting the ethylenically unsaturated intermediate of the formula Iawith an R_(F)-iodide using a free radical generating mechanism; and thenc) dehydrohalogenating the intermediate from step b) with an alkalimetal hydroxide, wherein R_(F), R₂, m and n are as defined in claim 1.6. An acrylate or methacrylate ester of formula II

wherein R_(F) is a straight or branched-chain perfluoroalkyl groupcontaining 4 to 20 carbon atoms, R₁ is hydrogen or methyl, R₂ is H or analkyl group with 1 to 4 carbon atoms, and m and n are, independently ofeach other, an integer from 2 to
 11. 7. An ester according to claim 6,wherein, R_(F) is a fully fluorinated, linear carbon chain with anaverage of about 4 to 16 carbon atoms, R₂ is hydrogen or an alkyl groupwith 1 to 2 carbon atoms, n is an integer from 5 to 10, and m is aninteger from 2 to
 6. 8. A process for the preparation of a copolymercomprising reacting a) 45-90% by weight of a monomer of formula II

wherein R_(F) is a straight or branched-chain perfluoroalkyl groupcontaining 4 to 20 carbon atoms, R₁ is H or CH₃, R₂ is H or an alkylgroup with 1 to 4 carbon atoms, and m and n are, independently of eachother, an integer from 2 to 11; and b) 5-30% by weight of a monomer offormula III(R₂)₂N—(CH₂)_(k)—X₁—C(═O)—C(R₁)═CH₂  (III) in which the nitrogen atom ispartially or completely quaternized or in the form of a salt and X₁ is Oor N(R₂) and wherein R₁ and R₂ are defined as above, each R₂ is the sameor different, and k is 2 to 4; and c) 0-10% by weight of at least onecopolymerizable nonfluorinated vinyl monomer, and, optionally, achain-transfer agent, in the presence of a free radical initiator.
 9. Amethod to impart oil and grease resistance to paper, which comprisesincorporating an amount of a copolymer that is effective to impart oiland grease resistance into the paper wherein the copolymer comprisesmonomers copolymerized in the following percentages by weight, relativeto the total weight of the copolymer: a) 45-90% by weight of a monomerof formula II

wherein R_(F) is a straight or branched-chain perfluoroalkyl groupcontaining 4 to 20 carbon atoms, R₁ is H or CH₃, R₂ is H or an alkylgroup with 1 to 4 carbon atoms, and m and n are, independently of eachother, an integer from 2 to 11; and b) 5-30% by weight of a monomer offormula III(R₂)₂N—(CH₂)_(k)—X₁—C(═O)—C(R₁)═CH₂  (III) in which the nitrogen atom ispartially or completely quaternized or in the form of a salt and X₁ is Oor N(R₂) and wherein R₁ and R₂ are defined as above, each R₂ is the sameor different, and k is 2 to 4, and c) 0-10% by weight of at least onecopolymerizable nonfluorinated vinyl monomer.
 10. A method according toclaim 9, wherein the copolymer is applied to dry paper through a coatingprocess in a size-press or by addition of the copolymer to an aqueouspulp.
 11. A method according to claim 9, wherein 0.02 to 1% by weight ofthe copolymer is applied, based on the dry weight of the paper or pulp.12. A method to impart soil-release and anti-soiling characteristics toa textile material, which comprises treating the textile material withan amount of a copolymer that is effective to impart soil-release andanti-soiling characteristics thereto wherein the copolymer comprisesmonomers copolymerized in the following percentages by weight, relativeto the total weight of the copolymer: a) 45-90% by weight of a monomerof formula II

wherein R_(F) is a straight or branched-chain perfluoroalkyl groupcontaining 4 to 20 carbon atoms, R₁ is H or CH₃, R₂ is H or an alkylgroup with 1 to 4 carbon atoms, and m and n are, independently of eachother, an integer from 2 to 11; and b) 5-30% by weight of a monomer offormula III(R₂)₂N—(CH₂)_(k)—X₁—C(═O)—C(R₁)═CH₂  (III) in which the nitrogen atom ispartially or completely quaternized or in the form of a salt and X₁ is Oor N(R₂) and wherein R₁ and R₂ are defined as above, each R₂ is the sameor different, and k is 2 to 4; and c) 0-10% by weight of at least onecopolymerizable nonfluorinated vinyl monomer.
 13. A method according toclaim 12, wherein the textile material is treated with 0.02 to 1% byweight of the copolymer, based on the weight of the dry textilematerial.
 14. A method according to claim 12, wherein the textilematerial is a carpet.
 15. Oil and grease resistant paper or pulp whichcomprises 0.02 to 1% by weight of a copolymer comprising monomerscopolymerized in the following percentages by weight, relative to thetotal weight of the copolymer: a) 45-90% by weight of a monomer offormula II

wherein R_(F) is a straight or branched-chain perfluoroalkyl groupcontaining 4 to 20 carbon atoms, R₁ is H or CH₃, R₂ is H or an alkylgroup with 1 to 4 carbon atoms, and m and n are, independently of eachother, an integer from 2 to 11; and b) 5-30% by weight of a monomer offormula III(R₂)₂N—(CH₂)_(k)—X₁—C(═O)—C(R₁)═CH₂  (III) in which the nitrogen atom ispartially or completely quaternized or in the form of a salt and X₁ is Oor N(R₂) and wherein R₁ and R₂ are defined as above, each R₂ is the sameor different, and k is 2 to 4; and c) 0-10% by weight of at least onecopolymerizable nonfluorinated vinyl monomer.
 16. Textile material,which comprises 0.02 to 1% by weight of a copolymer comprising monomerscopolymerized in the following percentages by weight, relative to thetotal weight of the copolymer: a) 45-90% by weight of a monomer offormula II

wherein R_(F) is a straight or branched-chain perfluoroalkyl groupcontaining 4 to 20 carbon atoms, R₁ is H or CH₃, R₂ is H or an alkylgroup with 1 to 4 carbon atoms, and m and n are, independently of eachother, an integer from 2 to 11; and b) 5-30% by weight of a monomer offormula III(R₂)₂N—(CH₂)_(k)—X₁—C(═O)—C(R₁)═CH₂  (III) in which the nitrogen atom ispartially or completely quaternized or in the form of a salt and X₁ is Oor N(R₂) and wherein R₁ and R₂ are defined as above, each R₂ is the sameor different, and k is 2 to 4; and c) 0-10% by weight of at least onecopolymerizable nonfluorinated vinyl monomer.
 17. A textile materialaccording to claim 16, which is selected from the group consisting ofcellulosics, polyamides, polyesters and polyolefins and blends thereof.18. A textile material according to claim 16, which is selected from thegroup consisting of cotton, nylon, wool, silk and polyester-cottonblends.
 19. A method of imparting oil and grease resistance to hardsubstrates, which comprises applying an amount of a copolymer that iseffective to impart oil and grease resistance onto the surface of thehard substrate wherein the copolymer comprises monomers copolymerized inthe following percentages by weight, relative to the total weight of thecopolymer: a) 45-90% by weight of a monomer of formula II

wherein R_(F) is a straight or branched-chain perfluoroalkyl groupcontaining 4 to 20 carbon atoms, R₁ is H or CH₃, R₂ is H or an alkylgroup with 1 to 4 carbon atoms, and m and n are, independently of eachother, an integer from 2 to 11; and b) 5-30% by weight of a monomer offormula III(R₂)₂N—(CH₂)_(k)—X₁—C(═O)—C(R₁)═CH₂  (III) in which the nitrogen atom ispartially or completely quaternized or in the form of a salt and X₁ is Oor N(R₂) and wherein R₁ and R₂ are defined as above, each R₂ is the sameor different, and k is 2 to 4; and c) 0-10% by weight of at least onecopolymerizable nonfluorinated vinyl monomer.